Photographic colour images from amino substituted phenols



Dec. 7, 1965 J. JAEKEN 3,222,176

PHOTOGRAPHIC COLOUR IMAGES FROM AMINO SUBSTITUTED PHENOLS Filed Oct. 2, 1961 nvvsuroz, JAN JAE/(EN United States Patent 3,222,176 PHOTOGRAPHIC COLOUR IMAGES FROM AMINO SUBSTITUTED PHENOLS Jan Jaeken, Hove-Antwerp, Belgium, assiguor to Gevaert Photo-Producten N.V., Mortsel, Belgium, a Belgian company n Filed Oct. 2, 1961, Ser. No. 142,334 Claims priority, application Belgium, Oct. 4, 1960, 40,105, Patent 595,694 2 Claims. (CI. 96-55) The present invention relates to a process for the manufacture of photographic colour images by colour development in the presence of a colour coupler, to photographic material containing such colour couplers and to photographic images obtained according to this process.

The process for the manufacture of photographic colour images by colour development consists therein that a silver salt image is developed in an exposed photographic material with an aromatic amino developing substance in the presence of a colour coupler. The colour coupler which may be present in the developing solution or in the photographic element, and the oxidation products of the aromatic amino developing substance formed during development, cooperate to produce a dyestufi image on the area where the silver image is developed.

The modern processes of colour photography are 'based upon the subtractive colour principle according to which differently sensitized silver halide emulsions are superposed in the form of layers. Each of these layers contains a diiferent colour coupler, so that by development in a solution containing an aromatic amine as developing substance a subtractive yellow, cyan and magenta dyestuii image is produced in the respective emulsion layers.

The colour couplers used to produce cyan dyestuffs, are generally phenols and naphthols and form indophenol dyestulfs upon coupling with the reaction product of the developing substance. I

It is known that orthoand meta-substituted aminophenols, e.g. those bearing an acylamino groups in the 2- or 5-position as described in the U.S. patent specification 2,772,162, may be used as cyan-forming colour couplers.

It has now been found that compounds corresponding to the general formula wherein one of the two symbols X and Y represents a -SO;,;R radical and the other a COR radical, wherein R represents an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkaryl group, a substituted alkaryl group, an aryl group, a substituted aryl group, a heterocyclic nucleus or a substituted heterocyclic nucleus, and whereby one of these su-bstituents contains a carbon chain with to 20 carbon atoms.

possess particularly interesting properties as cyan-forming colour couplers.

The preparation of such new colour couplers is illustrated hereinafter.

PREPARATION 1 A solution of 7.7 g. (0.05 mol) of 2-amino-5-nitrophenol and 6.9 g. (0.025 mol) of palmitoyl chloride in 50 cm. of acetone is allowed to stand for 1 hour. The solution is poured out in water. The formed precipitate is sucked oif, washed with hot water and recrystallized 3,222,175 Patented Dec. 7, 1965 from methanol toyield 8.2 g. of 2-palmitoylamino-5- nitrophenol.

Melting point: C.

18 g. (0.46 mol) of 2-palmitoylamino5-nitrophenol are reduced in dimethylformamide under hydrogen pressure and with Raney nickel as a catalyst. After pouring out in a sodium chloride solution, the formed precipitate is sucked off, and recrystallized from acetonitrile to yield 13 g. of 2-palmitoyl'amino-5aminophenol.

Melting point: 120 C.

32.6 g. (0.09 mol) of this amine and 16.5 g. (0.09 mol) of 2-thiophene sulphonyl chloride are allowed to stand for 2 hrs. in 110 cm. of pyridine. After pouring out in a mixture of diluted hydrochloric acid and ice, and. recrystallization of the obtained precipitate from ethyl acetate, 27.5 g. of colour coupler are obtained corresponding to the following formula Melting point: C.

PREPARATION 2 unooqom) 14-03,

Melting point: 138 C.

PREPARATION 3 Amixture of 77g. (0.5 mol) of Z-amino-S-nitrophenol, 105 .g. (0.55 mol) of p-toluene sulphonylchloride, 100 g. (1 mol) of calcium carbonate and 750 cm? of acetonitrile are refluxed for 90 min. After pouring out in water, sucking off, dissolution of the formed precipitate in cold 5 N aqueous sodium hydroxide, filtering oil, pouring out in 5 N aqueous hydrochloric acid, sucking off the formed precipitate, washing with water and recrystallization from toluene, 80 g. of Z-p-toluene-sulphonylamino-S-nitrophenol are obtained.

Melting point: C.

30.7 g. (0.1 mol) of this nitro compound are reduced in 240 cm. of ethanol with Raney nickel as 'a catalyst. After concentration of the solution and cooling, 17.6 g. of 2-p-toluene=sulphonylamino-5aammophenol are obtained.

Melting point: 198 C.

A mixture of 0.556 g. (0.002 mol) of this amine, 0.71 g. (0.002 mol) of 2-hexadecenyl succinic anhydride and 4 cm. of acetonitrile are refluxed for 1 h. After cooling, sucking off of the formed precipitate and washing with acetonitrile, 0.7 g. of colour coupler are obtained corresponding to the formula NHSOTOCHI Melting point: 98 C.

PREPARATION 4 A mixture of 46.2 g. (0.3 mol) of 2-amino-5-nitrophenol and 11.5 g. (0.1 mol) of methyl sulphonyl chloride in 150 cm. of acetonitrile, are refluxed for 90 min. The solvent is evaporated. On cooling the residue solidifies. After recrystallization from water containing active charcoal, 8.3 g. of Z-methyl-sulphonylamino-5-nitrophenol are obtained. Melting point: 176 C. After a second recrystallization, the melting point rises to 178 C.

11.5 g. (0.05 mol) of this nitro compound are reduced in ethanol under hydrogen pressure with Raney nickel as catalyst. After cooling, sucking off the formed precipitate and washing with a little ether, the amine is obtained. Melting point: 166 C. After strong concentration of the alcoholic filtrate, a second amount of amine is obtained. Melting point: 159 C. After recrystallization from ethanol, a total amount of 8 g. of a product is obtained with a melting point of 166 C.

0.5 g. (0.0025 mol) of 2-methyl sulphonylamino-S- aminophenol is dissolved in 8 cm. of acetonitrile. To this solution is added 0.55 g. (0.0025 mol) of lauroyl chloride and the mixture is refluxed for 1 hour. After cooling, sucking off of the formed precipitate and washing with a little acetonitrile and crystallization from acetonitrile, 0.7 g. of colour coupler is obtained corresponding to the formula V NHSOr-CH;

Melting point: 208 C.

PREPARATION 5 A solution of 69 g. (0.45 mol) of 2-amino5-nitrophenol and 27.4 g. (0.15 mol) of thienyl sulphonyl chloride in 225 cm. of acetonitrile is refluxed for 2 /2 h. After acidifying with hydrochloric gas or with etheric hydrochloric acid, the formed 2-amino-5-nitrophenol hydrochloride is sucked off. The acetonitrile filtrate is evaporated to dryness and then the residue is dissolved in cold 5 N aqueous sodium hydroxide. After filtering off the precipitation occurs on acidifying with hydrochloric acid. After sucking off, washing with N hydrochloric acid and recystallization from Water 21 g. of Z-thienyl sulphonylamino-S-nitrophenol are obtained.

Melting point: 178 C.

21 g. (0.07 mol) of this nitro compound are reduced in ethanol under hydrogen pressure with Raney nickel as a catalyst. After almost completely evaporating of the solvent, sucking off of the formed precipitate and washing with a little ether, 14 g. of 2-thienylsulphonylamino-5- aminophenol are obtained. Melting point: 155 C. After recrystallization from water the melting point remains at 155 C.

6.75 g. (0.025 mol) of this amino compound are dissolved in 80 cm. of acetonitrile. To this solution a solution is added of 5.5 g. (0.025 mol) of lauroyl chloride in 20 cm. of acetonitrile. The mixture is refluxed for 3 hours. After concentrating until half the volume, cooling, sucking off the formed precipitate, Washing with ether and recrystallization from ethanol, g. of colour coupler are obtained corresponding to the formula:

Melting point: 115 C.

The dyestuffs formed from this colour coupler are characterized by a very favourable absorption maximum. After development with an aromatic amino developing substance such as 2-methy1-4-diethylamino-aniline, they yield cyan dyestuffs with a bathochromatically shifted absorption maximum. Moreover, the dyestuffs obtained from the colour couplers according to the present invention are especially characterized by their excellent acid resistance. The bathochromic effect is especially prominent by the products containing a RSO NH- group in the 5-position.

Curve 1.-is the absorption curve of the dyestuff formed during development with 2-methyl-4-diethylamino-aniline in the presence of the colour coupler prepared according to Preparation 2.

Absorption maximum at about 660 m Curve 2.is the absorption curve of the dyestuff formed during development with 2-methyl-4-diethylamino-aniline in the presence of the colour coupler prepared according to the U.S. patent specification No. 2,772,162.

Q-o ONE.

Absorption maximum at about 640 me.

For carrying out the process according to the present invention, the colour couplers are incorporated into photographic silver halide emulsions prepared by means of usual colloids e.g. gelatin, polyvinyl alcohol, collodion or other natural or synthetic colloids e.g. those of the Belgian patent specification 568,153. These silver halide emulsions can be coated on a support consisting of paper, glass, nitrocellulose, cellulose ester such as cellulose triacetate, polyester, polystyrene or other natural or synthetic resins, and form part of a photographic material with one or more emulsion layers. Such a material is usually and essentially composed of superposed layers in the following sequence: a support, a red-sensitized emulsion layer having incorporated a cyan-forming colour coupler, a green-sensitized emulsion layer having incorporated therein a magenta-forming colour coupler and a blue-sensitive emulsion layer having incorporated therein a yellow-forming colour coupler. A yellow filter layer, which in most cases consists of colloidal silver, is usually applied between the blue-sensitive and the green-sensitized emulsion layer.

The new colour couplers are usually incorporated in the light-sensitive silver halide emulsion layer itself, but they can also be incorporated into an adjacent non-lightsensitive colloid layer or into a non-light-sensitive layer which is separated from the light-sensitive emulsion layer by a water-permeable colloid layer.

The aromatic amino compounds which can be used as a developing substance for such material comprise mono-, 70 diand triamino-aryl compounds, more especially N,N-

dialkyl-p-phenylenediamine and its derivatives such as N, N-dialkyl-N'-sulphomethyl-p-phenylene diamine and N, N-dialkyl-N'-carboxyrnethyl-p-phenylene diamine.

After exposure, the latent silver image in the different emulsion layers is converted by colour development into,

photographic material is fixed, rinsed and dried again.

The following example illustrates the present invention without limiting, however, the scope thereof.

Example A solution of 7 g. of colour coupler, obtained according to Preparation 2, in 53 cm. of ethanol and 17 cm. of N sodium hydroxide, is added to 0.5 kg. of a redsensitized silver bromide-iodide emulsion. The emulsion is brought to pH 6.5 by adding N acetic acid. After addition of the usual additives such as hardeners, wetting agents and stabilizing agents, the total weight is brought to 1 kg. by adding Water. The emulsion is cast onto the side of a cellulose triacetate support which is provided with an antihalation layer, and dried. Onto this emulsion layer are cast the following layers in the indicated sequence: a gelatin layer, a green-sensitized silver brornoiodide emulsion layer containing a magenta-forming colour coupler, a yellow filter layer consisting of a gelatin layer containing colloidal silver, an unsensitized bromoiodide emulsion layer containing a yellow-forming colour coupler, and an anti-stress layer. After exposing, the light-sensitive photographic material thus obtained is developed in a colour developing bath of the following Then this material is rinsed for 30 sec. and fixed in an acidic fixing bath of the following composition:

Sodium thiosulfate (anhydrous) g 200 Borax g 8 Sodium sulfite g 25 Potassium alum g 15 Boric acid g-.. 7.5 Water to cm. 1000 Now the material is rinsed for 10 min. and bleached in a bath of the following composition:

Potassium ferricyanide g 100 Potassium bromide g 25 Borax g 20 Boric acid -g 5 Water to cm. 1000 Finally the material is rinsed for 5 min. and fixed in a bath of the following composition:

Sodium thiosulfate (anhydrous) g Sodium sulfite g 10 Sodium carbonate g 14 Water to cm. 1000 In the red-sensitized emulsion layer, a cyan image is obtained having an absorption maximum at 660 m I claim:

1. A process for the production of photographic color images comprising the development in a photographic material of a latent silver salt image by means of a primary aromatic amino developing substance in the presence of a color coupler to form a cyan-colored indophenol dyestutf, said coupler having a formula selected from the group consisting of:

NHSOzR' NHCOR and and

RCONH RSOQNH wherein each of R and R is a radical selected from the group consisting of an alkyl radical, a carboxy substituted 'alkenyl radical, an alkyl phenyl radical and a thienyl radical, one of R and R comprising an aliphatic carbon chain of 10 to 20 carbon atoms.

References Cited by the Examiner UNITED STATES PATENTS 2,350,138 5/1944 Weissberger 96--55 2,536,010 12/1950 Schmidt et al 96-100 2,772,162 11/1956 Saminen et al 96-100 FOREIGN PATENTS 478,527 11/ 1951 Canada.

NORMAN G. TORCHIN, Primary Examiner.

HAROLD N. BURSTEIN, Examiner. 

1. A PROCESS FOR THE PRODUCTION OF PHOTOGRAPHIC COLOR IMAGES COMPRISING THE DEVELOPMENT IN A PHOTOGRAPHIC MATERIAL OF A LATENT SILVER SALT IMAGE BY MEANS OF A PRIMARY AROMATIC AMINO DEVELOPING SUBSTANCE IN THE PRESENCE OF A COLOR COUPLER TO FORM A CYAN-COLORED INDOPHENOL DYESTUFF, SAID COUPLER HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF; 